Hydrogenolysis catalysts with high acid tolerance

ABSTRACT

A catalyst includes a mixed metal oxide; an alumina; silica, and calcium, where the mixed metal oxide includes Cu and at least one of Mn, Zn, Ni, or Co. Such catalysts exhibit enhanced tolerance sulfur-containing compounds and free fatty acids.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/561,220, filed on Sep. 25, 2017, now U.S. Pat. No. 10,350,577, whichis a U.S. National Phase Application under 35 U.S.C. § 371 ofInternational Application No. PCT/US2016/024159, filed on Mar. 25, 2016,which claims benefit of priority to U.S. Provisional Application No.62/138,854, filed on Mar. 26, 2015, the entire contents of which areincorporated herein by reference in their entireties.

FIELD

The present technology relates generally to the field of hydrogenolysisand/or hydrogenation of feedstocks, wherein the feedstock includes atleast one carbonyl group. More specifically, the catalysts of thepresent technology are highly active for the hydrogenolysis of fattyacid methyl esters to produce fatty alcohols. The present technologyprovides catalysts that exhibit remarkable acid impurity tolerance aswell as methods of making the catalysts and processes involving thecatalysts.

BACKGROUND

Current commercial catalysts for hydrogenolysis of fatty acid estersutilize CuCr tablets. These catalysts are activated with hydrogen toreduce the CuO to form what is commonly believed to be the active site.Without being bound by theory, it is believed the active site involvesCu^(o). The feed for producing fatty alcohols may contain impurities,such as, but not limited to, sulfur or free fatty acids (FFAs). Sulfurcan poison Cu^(o) active sites in the catalyst, thereby deactivating thecatalyst. FFAs may compete for adsorption sites where esterhydrogenolysis takes place, thereby significantly inhibiting the rate ofester hydrogenolysis (a reversible deactivation). FFAs may alsoaccelerate the Cu^(o) crystallite growth thereby causing activity loss(a permanent deactivation). The main causes of catalyst deactivationare: copper crystallite growth, sulfur, and coke deposition.

SUMMARY

In one aspect, a catalyst is provided that includes a mixed metal oxide,alumina; silica; and calcium, where the mixed metal oxide includes Cuand at least one of Mn, Zn, Ni, or Co. In some embodiments, the copperdispersion of the activated catalyst is from about 0.5% to about 20%.

In some embodiments, the catalyst includes about 15 wt % to about 50 wt% Cu. In some embodiments, the mixed metal oxide includes Cu and Mn. Insome embodiments, the mixed metal oxide includes Cu and Mn, and thecatalyst includes about 2 wt % to about 10 wt % Mn. In some embodiments,the mixed metal oxide includes Cu and Zn. In some embodiments, the mixedmetal oxide includes Cu and Zn, and the catalyst includes about 15 wt %to about 50 wt % Zn.

In some embodiments, the amount of the alumina in the catalyst is fromabout 10 wt % to about 30 wt %. In some embodiments, the amount of thesilica in the catalyst is from about 10 wt % to about 30 wt %. In someembodiments, the amount of the calcium in the catalyst is from about 2wt % to about 10 wt %. In some embodiments, the catalyst issubstantially free of sodium. In some embodiments, the catalyst issubstantially free of chromium. In some embodiments, the catalyst issubstantially free of barium.

In some embodiments, the catalyst has a Brunauer-Emmett-Teller surfacearea from about 10 m²/g to about 150 m²/g. In some embodiments, thecatalyst has a Brunauer-Emmett-Teller surface area from about 10 m²/g toabout 70 m²/g. In some embodiments, the catalyst has a mercury porevolume from about 0.10 cm³/g to about 0.80 cm³/g. In some embodiments,the catalyst has a packed ambient bulk density from about 0.3 g/cm³ toabout 1.6 g/cm³. In some embodiments, the catalyst has a side crushstrength from about 2.5 lbs/mm to about 12 lbs/mm.

In some embodiments, the catalyst is in a shape includes at least one ofcylindrical, tubular, polylobular, fluted, or ridged. In someembodiments, the catalyst has a diameter from about 0.5 mm to about 3.0mm. In some embodiments, the diameter is from about 1.0 mm to about 2.0mm.

In an aspect, a method of making the catalyst of any of the aboveembodiments is provided where the method includes calcining a shapedmaterial. The shaped material is formed by shaping a paste, the pasteincluding a Cu oxide and at least one metal oxide of Mn, Zn, Ni, or Co;an alumina; a silica sol; and calcium hydroxide. In some embodiments,the paste further includes a solvent. In some embodiments, the pastefurther includes a clay material. In some embodiments, the shapedmaterial is prepared by tableting or extruding the paste. In someembodiments, the paste further includes an extrusion aid. In someembodiments, the extrusion aid includes a polysaccharide. In someembodiments, the Cu oxide includes cupric oxide. In some embodiments,the calcining comprises a temperature from about 300° C. to about 1,000°C. In some embodiments, the duration of the calcining step is about 15minutes to about 12 hours. In some embodiments, the shaped material isdried prior to calcining. In some embodiments, the shaped material isdried at a temperature from about 40° C. to about 250° C.

In an aspect, process is provided where the process involveshydrogenating a feedstock by contacting the feedstock and H₂ with thecatalyst of any one of the above described embodiments, wherein thefeedstock includes at least one carbonyl group. In some embodiments, thefeedstock includes compounds where the longest carbon chain has a carbonnumber from C₈-C₁₈. In some embodiments, the feedstock includes fattyacid methyl esters. In some embodiments, the feedstock includes freefatty acids.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the hydrogenolysis performance of one embodiment of acatalyst of the present technology for a C₁₂-C₁₄ fatty acid methyl ester(C₁₂-C₁₄ FAME) feed in comparison to a CuCrMn catalyst, according to theworking examples.

FIG. 2 illustrates the hydrogenolysis productivity per kilogram of oneembodiment of a catalyst of the present technology for a C₁₂-C₁₄ FAMEfeed in comparison to a tabletted CuMn catalyst, according to theworking examples.

FIG. 3 illustrates the hydrogenolysis performance of two embodiments ofcatalysts of the present technology for a C₁₆-C₁₈ fatty acid methylester (C₁₆-C₁₈ FAME) feed in comparison to a CuCrMn catalyst, accordingto the working examples.

DETAILED DESCRIPTION

The following terms are used throughout as defined below.

As used herein and in the appended claims, singular articles such as “a”and “an” and “the” and similar referents in the context of describingthe elements (especially in the context of the following claims) are tobe construed to cover both the singular and the plural, unless otherwiseindicated herein or clearly contradicted by context. Recitation ofranges of values herein are merely intended to serve as a shorthandmethod of referring individually to each separate value falling withinthe range, unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the embodiments and does not pose a limitation on the scopeof the claims unless otherwise stated. No language in the specificationshould be construed as indicating any non-claimed element as essential.

As used herein, “about” will be understood by persons of ordinary skillin the art and will vary to some extent depending upon the context inwhich it is used. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “about” will mean up to plus or minus 10% of the particular term.

Generally, reference to a certain element such as hydrogen or H is meantto include all isotopes of that element. For example, if an R group isdefined to include hydrogen or H, it also includes deuterium andtritium. Compounds comprising radioisotopes such as tritium, C¹⁴, P³²and S³⁵ are thus within the scope of the present technology. Proceduresfor inserting such labels into the compounds of the present technologywill be readily apparent to those skilled in the art based on thedisclosure herein.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the likeinclude the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember. Thus, for example, a group having 1-3 atoms refers to groupshaving 1, 2, or 3 atoms. Similarly, a group having 1-5 atoms refers togroups having 1, 2, 3, 4, or 5 atoms, and so forth.

“Substantially free” as used herein will be understood by persons ofordinary skill in the art and will vary to some extent depending uponthe context. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “substantially free” will mean that the substance is at about 0.5wt % or less.

Fatty alcohols, also commonly referred to as detergent alcohols, arechemical intermediates used in the oleochemical industry formanufacturing detergents, cosmetics, and industrial waxes. The fattyalcohols are monohydric aliphatic alcohols of 6 to 34 atoms. They may beproduced by oleochemical routes that involve hydrogenolysis of esters ofpalm or coconut oils to alcohols, petrochemical processes that involveoligomerization, and/or hydroformylation followed by oxo-aldehydehydrogenation to alcohols. Fatty alcohols may also be made frompetrochemical feed stocks.

Catalysts have been identified, and are described herein, that, whenused in a hydrogenation and/or hydrogenolysis reaction to produce fattyalcohols, exhibit high tolerance to sulfur and FFAs. The catalyst may beconverted to other, more active catalytic species, either prior to acatalyzed reaction, or during the course of a catalyzed reaction bycontacting the catalyst with H₂ at about 150° C. to about 250° C. Forexample, while copper oxide possesses some hydrogenolysis activity,during the course of a hydrogenolysis reaction converting a Cu fattyacid ester to dodecanol under hydrogen pressure it may be that at leastsome copper oxide is converted to a species more active in thehydrogenolysis of the Cu fatty acid ester. For example, and withoutbeing bound by theory, it is believed that the more active species inhydrogenation and hydrogenolysis involves Cu^(o). Such a reduction toprovide a portion of the composition with a more catalytically activecomponent may also be carried out in advance of the hydrogenation and/orhydrogenolysis reaction by contacting the catalyst with H₂ prior to thehydrogenation and/or hydrogenolysis reaction.

The catalysts include a mixed metal oxide, alumina, silica, and calcium,where the mixed metal oxide includes Cu and at least one of Mn, Zn, Ni,or Co. The catalyst may include about 15 wt % to about 50 wt % Cu. Theamount of Cu in the catalyst may be about 15 wt %, about 16 wt %, about17 wt %, about 18 wt %, about 19 wt %, about 20 wt %, about 21 wt %,about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt %, about 26 wt%, about 27 wt %, about 28 wt %, about 29 wt %, about 30 wt %, about 31wt %, about 32 wt %, about 33 wt %, about 34 wt %, about 35 wt %, about36 wt %, about 37 wt %, about 38 wt %, about 39 wt %, about 40 wt %,about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt %, about 45 wt%, about 46 wt %, about 47 wt %, about 48 wt %, about 49 wt %, about 50wt % as well as any range including, and in between, any two of thesevalues. For example, the catalyst may include about 26 wt % to about 40wt % Cu.

As disclosed above, the mixed metal oxide also includes at least one ofMn, Zn, Ni, or Co. Thus, the mixed metal oxide may include Mn, Zn, Ni,Co, or a combination of any two or more thereof in addition to the Cu.The catalyst may include about 1 wt % to about 30 wt % of Mn, Zn, Ni,Co, or combination of any two or more thereof. The amount of Mn, Zn, Ni,or Co, or the combination of any two or more thereof in the catalyst,may be about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about19 wt %, about 20 wt %, about 21 wt %, about 22 wt %, about 23 wt %,about 24 wt %, about 25 wt %, about 26 wt %, about 27 wt %, about 28 wt%, about 29 wt %, about 30 wt %, or any range including and in betweenany two of these values.

In any of the above embodiments, the “copper dispersion” of the catalystmay be from about 0.5% to about 20%. “Copper dispersion” is defined asthe ratio, commonly reported as percentage, of the Cu atoms accessiblevia gaseous diffusion of gas molecules such as N₂O (i.e., surfaceexposed atoms) to total number of Cu atoms of the catalyst. This ratiorepresents the percent of Cu at the surface available to catalyzechemical reactions in relation to total bulk Cu content of the catalyst.The copper dispersion of any of the catalysts described herein may beabout 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1.0%,about 1.2%, about 1.4%, about 1.6%, about 1.8%, about 2.0%, about 2.2%,about 2.4%, about 2.6%, about 2.8%, about 3.0%, about 3.2%, about 3.4%,about 3.6%, about 3.8%, about 4.0%, about 4.2%, about 4.4%, about 4.6%,about 4.8%, about 5.0%, about 5.2%, about 5.4%, about 5.6%, about 5.8%,about 6.0%, about 6.2%, about 6.4%, about 6.6%, about 6.8%, about 7.0%,about 7.2%, about 7.4%, about 7.6%, about 7.8%, about 8.0%, about 8.2%,about 8.4%, about 8.6%, about 8.8%, about 9.0%, about 9.2%, about 9.4%,about 9.6%, about 9.8%, about 10.0%, about 10.5%, about 11%, about11.5%, about 12.0%, about 12.5%, about 13.0%, about 13.5%, about 14.0%,about 14.5%, about 15.0%, about 15.5%, about 16.0%, about 16.5%, about17.0%, about 17.5%, about 18.0%, about 18.5%, about 19.0%, about 19.5%,about 20%, or any range including and in between any two of thesevalues.

Methods of determining copper dispersion of a catalyst, include, but arenot limited to, the methods described in Evans, J. W. et al. “On theDetermination of Copper Surface Area by Reaction with Nitrous Oxide,”Applied Catalysis, 1983, 7, 75-83; Amorim de Carvalho, M. C. N. et al.“Quantification of metallic area of high dispersed copper on ZSM-5catalyst by TPD of H₂ ,’” Catalysis Communications, 2002, 3, 503-509;Sato, S. et al. “Distinction Between Surface and Bulk Oxidation of Cuthrough N₂O Decomposition,” Journal of Catalysis, 2000, 196, 195-199;Jensen, J. R. et al. “An Improved N₂O-method for measuringCu-dispersion,” Applied Catalysis A, 2004, 266, 117-122; and Gervasini,A., Gennici, S., “Dispersion and surface states of copper catalysts bytemperature-programmed-reduction of oxidized surfaces (s-TPR),” AppliedCatalysis A, 2005, 281, 199-205, each of which is incorporated herein byreference in its entirety for any and all purposes.

One procedure for determining Cu dispersion and Cu surface area is asfollows: a calcined catalyst is reduced at 210° C. for 90 minutes aftera 5° C./min ramp in 5% H₂/95% N₂ gas. The reduced catalyst is cooled to60° C. and held at that temperature for 15 minutes while it is purgedwith He. At 60° C., 2% N₂O/98% He is passed over the reduced catalystand the evolution of N₂ is observed by a thermal conductivity detectorin conjunction with a liquid Ar cooled trap which condenses unreactedN₂O. The measurement is completed when no further N₂ is evolved. Theamount of N₂O consumed and N₂ evolved is assumed to follow the reactionchemistry N₂O+2Cu→N₂+Cu₂O on the surface of the reduced catalyst; thereaction does occur in the bulk (i.e., subsurface) Cu layers. The Cudispersion is then calculated by taking the ratio of surface Cu atomsper gram catalyst measured by this method (i.e. atoms N₂ evolvedmultiplied by 2) divided by the total number of Cu atoms per gramcatalyst.

In any of the above embodiments, the mixed metal oxide may include Cuand Mn. In any of the above embodiments, the mixed metal oxide mayinclude Cu and Mn, and the catalyst may include about 2 wt % to about 10wt % Mn. The amount of Mn in the catalyst may be about 2 wt %, about 3wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt%, about 9 wt %, about 10 wt %, or any range including and in betweenany two of these values. For example, in any of the embodimentsdescribed herein the mixed metal oxide may include Cu and Mn, and thecatalyst may include about 2 wt % to about 6 wt % Mn.

In any of the above embodiments, the mixed metal oxide may include Cuand Zn. In any of the above embodiments, the mixed metal oxide mayinclude Cu and Zn, and the catalyst may include about 15 wt % to about50 wt % Zn. The amount of Zn in the catalyst may be about 15 wt %, about16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, about 20 wt %,about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt%, about 26 wt %, about 27 wt %, about 28 wt %, about 29 wt %, about 30wt %, about 31 wt %, about 32 wt %, about 33 wt %, about 34 wt %, about35 wt %, about 36 wt %, about 37 wt %, about 38 wt %, about 39 wt %,about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt%, about 45 wt %, about 46 wt %, about 47 wt %, about 48 wt %, about 49wt %, about 50 wt %, or any range including and in between any two ofthese values. For example, the catalyst may include about 15 wt % toabout 25 wt % Zn.

The amount of the alumina in the catalyst may be from about 10 wt % toabout 30 wt %. The amount of the alumina in the catalyst may be about 10wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %,about 20 wt %, about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt%, about 25 wt %, about 26 wt %, about 27 wt %, about 28 wt %, about 29wt %, about 30 wt %, or any range including and in between any two ofthese values. For example, the amount of the alumina in the catalyst maybe about 15 wt % to about 25 wt %.

The amount of the silica in the catalyst may be from about 10 wt % toabout 30 wt %. The amount of the silica in the catalyst may be about 10wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %,about 20 wt %, about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt%, about 25 wt %, about 26 wt %, about 27 wt %, about 28 wt %, about 29wt %, about 30 wt %, or any range including and in between any two ofthese values. For example, the amount of the silica in the catalyst maybe about 15 wt % to about 25 wt %.

The amount of the calcium in the catalyst may be from about 2 wt % toabout 10 wt %. The amount of calcium in the catalyst may be about 2 wt%, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %,about 8 wt %, about 9 wt %, about 10 wt %, or any range including and inbetween any two of these values. For example, it may be that in any ofthe embodiments described herein that the amount of calcium in thecatalyst is from about 3 wt % to about 8 wt %.

The catalyst may be substantially free of sodium. In any of the aboveembodiments, the amount of sodium in the catalyst may be less than about0.4 wt %, less than about 0.3 wt %, less than about 0.2 wt %, less thanabout 0.1 wt %, or any range including and in between any two of thesevalues. In any of the above embodiments, the catalyst may besubstantially free of chromium. In any of the above embodiments, theamount of chromium in the catalyst may be less than about 0.4 wt %, lessthan about 0.3 wt %, less than about 0.2 wt %, less than about 0.1 wt %,or any range including and in between any two of these values. In any ofthe above embodiments, the catalyst may be substantially free of barium.In any of the above embodiments, the amount of barium in the catalystmay be less than about 0.4 wt %, less than about 0.3 wt %, less thanabout 0.2 wt %, less than about 0.1 wt %, or any range including and inbetween any two of these values.

The catalyst may have a Brunauer-Emmett-Teller surface area (“BETsurface area”) from about 10 m²/g to about 150 m²/g. The BET surfacearea may be determined by several methods, including the methoddescribed in ASTM-D3663-03 (2008), incorporated herein by reference inits entirety for any and all purposes. The BET surface area may be about10 m²/g, about 12 m²/g, about 14 m²/g, about 16 m²/g, about 18 m²/g,about 20 m²/g, about 22 m²/g, about 24 m²/g, about 26 m²/g, about 28m²/g, about 30 m²/g, about 32 m²/g, about 34 m²/g, about 36 m²/g, about38 m²/g, about 40 m²/g, about 42 m²/g, about 44 m²/g, about 46 m²/g,about 48 m²/g, about 50 m²/g, about 52 m²/g, about 54 m²/g, about 56m²/g, about 58 m²/g, about 60 m²/g, about 62 m²/g, about 64 m²/g, about66 m²/g, about 68 m²/g, about 70 m²/g, about 72 m²/g, about 74 m²/g,about 76 m²/g, about 78 m²/g, about 80 m²/g, about 82 m²/g, about 84m²/g, about 86 m²/g, about 88 m²/g, about 90 m²/g, about 92 m²/g, about94 m²/g, about 96 m²/g, about 98 m²/g, about 100 m²/g, about 102 m²/g,about 104 m²/g, about 106 m²/g, about 108 m²/g, about 110 m²/g, about112 m²/g, about 114 m²/g, about 116 m²/g, about 118 m²/g, about 120m²/g, about 122 m²/g, about 124 m²/g, about 126 m²/g, about 128 m²/g,about 130 m²/g, about 132 m²/g, about 134 m²/g, about 136 m²/g, about138 m²/g, about 140 m²/g, about 142 m²/g, about 144 m²/g, about 146m²/g, about 148 m²/g, about 150 m²/g, or any range including and inbetween any two of these values. For example, in any of the aboveembodiments, the catalyst may have a BET surface area from about 10 m²/gto about 70 m²/g.

The catalyst may have a mercury pore volume from about 0.10 cm³/g toabout 0.80 cm³/g. The mercury pore volume may be determined by a varietyof methods, including, but are not limited to, the method described inASTM-D4284-12, incorporated herein by reference in its entirety for anyand all purposes. The mercury pore volume may be about 0.10 cm³/g, about0.15 cm³/g, about 0.20 cm³/g, about 0.25 cm³/g, about 0.30 cm³/g, about0.35 cm³/g, about 0.40 cm³/g, about 0.45 cm³/g, about 0.50 cm³/g, about0.55 cm³/g, about 0.60 cm³/g, about 0.65 cm³/g, about 0.70 cm³/g, about0.75 cm³/g, about 0.80 cm³/g, or any range including and in between anytwo of these values.

The catalyst may have a packed ambient bulk density from about 0.3 g/cm³to about 1.6 g/cm³. The packed ambient bulk density may be determined bya variety of methods, including, but are not limited to, the methoddescribed in ASTM-D4164-82, incorporated herein by reference in itsentirety for any and all purposes. The packed ambient bulk density maybe about 0.3, about 0.4 g/cm³, about 0.5 g/cm³, about 0.6 g/cm³, about0.7 g/cm³, about 0.8 g/cm³, about 0.9 g/cm³, about 1.0 g/cm³, about 1.1g/cm³, about 1.2 g/cm³, about 1.3 g/cm³, about 1.4 g/cm³, about 1.5g/cm³, about 1.6 g/cm³, or any range including and in between any two ofthese values.

The catalyst may have a side crush strength from about 2.5 lbs/mm toabout 12 lbs/mm. Side crush strength may be determined according toASTM-04179-82, incorporated herein by reference in its entirety for anyand all purposes, as well as other methods well-known to one of skill inthe art. The side crush strength may be about 2.5 lbs/mm, about 3.0lbs/mm, about 3.5 lbs/mm, about 4.0 lbs/mm, about 4.5 lbs/mm, about 5.0lbs/mm, about 5.5 lbs/mm, about 6.0 lbs/mm, about 6.5 lbs/mm, about 7.0lbs/mm, about 7.5 lbs/mm, about 8.0 lbs/mm, about 8.5 lbs/mm, about 9.0lbs/mm, about 9.5 lbs/mm, about 10.0 lbs/mm, about 10.5 lbs/mm, about11.0 lbs/mm, about 11.5 lbs/mm, about 12 lbs/mm, or any range includingand in between any two of these values.

The catalyst may be in a shape that includes at least one ofcylindrical, tubular, polylobular, fluted, or ridged. In any of theabove embodiments, the catalyst may have a diameter from about 0.5 mm toabout 3.0 mm. The diameter of the catalyst may be about 0.5 mm, about0.6 mm, about 0.7 mm, about 0.8 mm, about 0.9 mm, about 1.0 mm, about1.1 mm, about 1.2 mm, about 1.3 mm, about 1.4 mm, about 1.5 mm, about1.6 mm, about 1.7 mm, about 1.8 mm, about 1.9 mm, about 2.0 mm, about2.1 mm, about 2.2 mm, about 2.3 mm, about 2.4 mm, about 2.5 mm, about2.6 mm, about 2.7 mm, about 2.8 mm, about 2.9 mm, about 3.0 mm, or anyrange including and in between any two of these values. For example, itmay be that the catalyst has a diameter from about 1.0 mm to about 2.0mm.

In another aspect, a method of making any of the above catalysts isprovided, where the process includes calcining a shaped material. Theshaped material is formed by shaping a paste. The paste of the methodincludes a Cu oxide and at least one metal oxide of Mn, Zn, Ni, or Co;an alumina; a silica sol; and calcium hydroxide. The calcium hydroxidemay arise from combining precursors, such as a calcium salt and ahydroxide source. It is also contemplated the metal oxide of the processmay arise from a precursor that provides the metal oxide. Suchprecursors include, but not limited, to carbonates and nitrates of themetals. In any of the above embodiments, it may be the Cu oxide includescupric oxide.

The paste may further include a clay material, such as, but not limitedto, an alumina-silicate clay. Alumina-silicate clays include, but arenot limited to, attapulgites, sepiolites, serpentines, kaolinites,calcium montmorillonites, and mixtures of any two or more thereof. Suchalumina-silicate clays may include clays obtained from theMeigs-Attapulgus-Quincy fullers earth districts, located in southwestGeorgia and northern Florida. The term “attapulgite” is used to refer tochain lattice type clay minerals, encompassing minerals and mineralgroups variously referred to by those skilled in the art as“attapulgite,” “palygorskite,” “sepiolite,” and “hormite.” In any of theabove embodiments, the clay material includes attapulgite. In any of theabove embodiments, the attapulgite is present as the largest componentby mass of the clay material. The clay material may be undried, dried,or calcined. It may be the free moisture content of the clay material isfrom about 3 wt % to about 8 wt % of the clay material, where“free-moisture content” refers to the amount of water removed from theclay material by heating at about 105° C. (220° F.) until a constantweight is maintained. In any of the above embodiments of the process,the clay material may be powdered. In any of the above embodiments, theclay material may be powdered and have mesh size less than about 200mesh (U.S. Standard). In any of the above embodiments, the clay materialmay be powdered and have mesh size less than about 325 mesh (U.S.Standard).

In any embodiment of the methods described herein, the paste may furtherinclude a solvent. The solvent may include water, an alcohol (e.g.,methanol, ethanol, propanol), a ketone (e.g., acetone, methyl ethylketone), an aldehyde (e.g., propanol, butanal), or a mixture of any twoor more thereof. In any of the above embodiments, the solvent mayinclude water. The amount of solvent used is an amount that provides aconsistency which allows for a shape to be formed out of the paste, butnot so fluid as to fail to hold the formed shape. Typically, the totalamount of solvent in the paste, including that contributed by othercomponents (e.g., water from a clay) is from about 15 wt % to about 60%by weight of the paste. The total amount of solvent in the paste may beabout 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt%, about 20 wt %, about 22 wt %, about 24 wt %, about 26 wt %, about 28wt %, about 30 wt %, about 32 wt %, about 34 wt %, about 36 wt %, about38 wt %, about 40 wt %, about 42 wt %, about 44 wt %, about 46 wt %,about 48 wt %, about 50 wt %, about 52 wt %, about 54 wt %, about 56 wt%, about 58 wt %, about 60 wt %, or any range including and in betweenany two of these values. In any of the above embodiments of the method,it may be that the total amount of solvent is from about 35 wt % toabout 55 wt % of the paste.

In any of the above embodiments, the shaped material may be prepared bytableting or extruding the paste. In any of the above embodiments, theshape may include at least one of cylindrical, tubular, polylobular,fluted, or ridged. In any of the above embodiments, it may be the pasteincludes a rheology control agent and/or a pore forming agent. Rheologycontrol agents include, but are not limited to, starches, sugars,glycols, polyols, powdered organic polymers, graphite, stearic acid andits esters. Pore forming agents include, but are not limited to,graphite, polypropylene or other organic polymer powders, activatedcarbon, charcoal, sugars, starches and cellulose flour. The rheologycontrol agent and/or pore forming agent may be present in an amount offrom about 0.5 wt % to about 20 wt % of the paste. In any of the aboveembodiments, it may be the rheology control agent is an extrusion aid.In any of the above embodiments, it may be the extrusion aid includes apolysaccharide.

The calcining may include heating at a temperature from about 300° C. toabout 1,000° C. The calcining temperature may be about 300° C., about350° C., about 400° C., about 450° C., about 500° C., about 550° C.,about 600° C., about 650° C., about 700° C., about 750° C., about 800°C., about 850° C., about 900° C., about 950° C., about 1,000° C., or anyrange including and in between any two of these values. In any of theabove embodiments, it may be the duration of the calcining step is about15 minutes to about 12 hours. The duration of the calcining step may beabout 15 minutes, about 30 minutes, about 45 minutes, about 1 hour,about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about10 hours, about 11 hours, about 12 hours, or any range including and inbetween any two of these values. In any of the above embodiments, it maybe the shaped material is dried prior to calcining. In any of the aboveembodiments, it may be the shaped material is dried at a temperaturefrom about 40° C. to about 250° C. The shaped material may be dried at atemperature of about 40° C., about 50° C., about 60° C., about 70° C.,about 80° C., about 90° C., about 100° C., about 125° C., about 150° C.,about 175° C., about 200° C., about 225° C., about 250° C., or any rangeincluding and in between any two of these values.

In another aspect, a process is provided for hydrogenation and/orhydrogenolysis of a feedstock by contacting the feedstock and H₂ and anyof the above catalysts, wherein the feedstock includes at least onecarbonyl group. In many embodiments, the process may includehydrogenolysis of the feedstock. Feedstocks are compounds with at leastone carbonyl group (such as ketones, aldehydes, esters, and carboxylicacids). The feedstock may also include one or more other functionalgroups that contain one or more π bonds, such as a carbon-carbon doublebond, a carbon-carbon triple bond, a carbon-heteroatom double bond, or acarbon-heteroatom triple bond. Functional groups containing a π bondinclude, but are not limited to, alkenes, alkynes, carbonyls, nitrogroups, and nitriles. Feedstocks therefore include, but are not limitedto, free fatty acids, fatty acid esters (including mono-, di-, andtriglycerides), or combinations thereof. In any of the aboveembodiments, it may be the fatty acid ester includes a fatty acid methylester, a fatty acid ethyl ester, a fatty acid propyl ester, a fatty acidbutyl ester, or mixtures of any two or more thereof. The free fattyacids, fatty acid esters, or combinations thereof may be derived fromanimal fats, animal oils, plant fats, plant oils, vegetable fats,vegetable oils, or mixtures of any two or more thereof. Plant and/orvegetable oils include, but are not limited to, soybean oil, canola oil,coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palmoil fatty acid distillate, palm kernel oil, jatropha oil, sunflower oil,castor oil, camelina oil, algae oil, seaweed oil, oils from halophiles,and mixtures of any two or more thereof. Animal fats and/or oils as usedabove includes, but is not limited to, inedible tallow, edible tallow,technical tallow, floatation tallow, lard, poultry fat, poultry oils,fish fat, fish oils, and mixtures of any two or more thereof. In any ofthe above embodiments of the process, the free fatty acids, fatty acidesters, or combinations thereof include a hydrogenated animal fat,animal oil, plant fat, plant oil, vegetable fat, vegetable oil, ormixture of any two or more thereof. In any of the above embodiments, thefeedstock may include fatty acid methyl esters. Such fatty acid methylesters may be formed by esterification of free fatty acids with methanolor transesterification of fatty acid esters with methanol. In any of theabove embodiments, it may be the feedstock includes free fatty acids.The free fatty acids may be from about 0.1 wt % to about 10 wt % of thefeedstock. Therefore, the amount of free fatty acids in the feedstockmay be about 0.1 wt %, about 0.2 wt %, about 0.3 wt %, about 0.4 wt %,about 0.5 wt %, about 0.6 wt %, about 0.7 wt %, about 0.8 wt %, about0.9 wt %, about 1.0 wt %, about 1.2 wt %, about 1.4 wt %, about 1.6 wt%, about 1.8 wt %, about 2.0 wt %, about 2.2 wt %, about 2.4 wt %, about2.6 wt %, about 2.8 wt %, about 3.0 wt %, about 3.2 wt %, about 3.4 wt%, about 3.6 wt %, about 3.8 wt %, about 4.0 wt %, about 4.2 wt %, about4.4 wt %, about 4.6 wt %, about 4.8 wt %, about 5.0 wt %, about 5.5 wt%, about 6.0 wt %, about 6.5 wt %, about 7.0 wt %, about 7.5 wt %, about8.0 wt %, about 8.5 wt %, about 9.0 wt %, about 10.0 wt %, or any rangeincluding and in between any two of these values.

In any of the above embodiments, the feedstock includes compounds wherethe longest carbon chain has a carbon number from C₈-C₁₈. Thus, thefeedstock may include a compound where the longest carbon chain has acarbon number of C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, orany range including and in between any two of these values. In any ofthe above embodiments, the feedstock may include a compound where thelongest carbon chain has with a carbon number of C₁₂-C₁₈. In any of theabove embodiments, the feedstock may include fatty acid methyl esterswhere the longest carbon chain has a carbon number from C₅-C₁₈. In anyof the above embodiments, it may be the feedstock includes at least oneof methyl laurate, methyl myristate, methyl palmitate, or methylstearate. In any of the above embodiments, it may be the processinvolves producing a fatty alcohol. The fatty alcohol may have a carbonnumber from C₈-C₁₈. Thus, the fatty alcohol may have a carbon number ofC₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, or include fattyalcohols with a carbon number including and in between any two of thesevalues.

The molar ratio of the H₂ to the feedstock may be from about 100:1 toabout 2000:1. In any of the above embodiments, the hydrogenation and/orhydrogenolysis may occur at a temperature from about 100° C. to about350° C. The temperature of the process may be about 100° C., about 150°C., about 200° C., about 250° C., about 300° C., about 350° C., or anyrange including or in between any two of these values. In any of theabove embodiments, the hydrogenation and/or hydrogenolysis may occur ata pressure from about 1 bar to about 60 bar. The hydrogenation and/orhydrogenolysis pressure may be independent from each other, and may beabout 1 bar, about 2 bar, about 3 bar, about 4 bar, about 5 bar, about 6bar, about 7 bar, about 8 bar, about 9 bar, about 10 bar, about 12 bar,about 14 bar, about 16 bar, about 18 bar, about 20 bar, about 22 bar,about 24 bar, about 26 bar, about 28 bar, about 30 bar, about 32 bar,about 34 bar, about 36 bar, about 38 bar, about 40 bar, about 42 bar,about 44 bar, about 46 bar, about 48 bar, about 50 bar, about 52 bar,about 54 bar, about 56 bar, about 58 bar, about 60 bar, or any rangeincluding and in between any two of these values. In any of the aboveembodiments, contacting the feedstock and H₂ with the catalyst of thepresent technology may involve flowing the feedstock and H₂ at a liquidhourly space velocity (“LHSV”) of about 0.1 hr⁻¹ to about 10.0 hr⁻¹. TheLHSV may be about 0.1 hr⁻¹, about 0.2 hr⁻¹, about 0.3 hr⁻¹, about 0.4hr⁻¹, about 0.5 hr⁻¹, about 0.6 hr⁻¹, about 0.7 hr⁻¹, about 0.8 hr⁻¹,about 0.9 hr⁻¹, about 1.0 hr⁻¹, about 1.2 hr⁻¹, about 1.4 hr⁻¹, about1.6 hr⁻¹, about 1.8 hr⁻¹, about 2.0 hr⁻¹, about 2.2 hr⁻¹, about 2.4hr⁻¹, about 2.6 hr⁻¹, about 2.8 hr⁻¹, about 3.0 hr⁻¹, about 3.2 hr⁻¹,about 3.4 hr⁻¹, about 3.6 hr⁻¹, about 3.8 hr⁻¹, about 4.0 hr⁻¹, about4.2 hr⁻¹, about 4.4 hr⁻¹, about 4.6 hr⁻¹, about 4.8 hr⁻¹, about 5.0hr⁻¹, about 5.5 hr⁻¹, about 6.0 hr⁻¹, about 6.5 hr⁻¹, about 7.0 hr⁻¹,about 7.5 hr⁻¹, about 8.0 hr⁻¹, about 8.5 hr⁻¹, about 9.0 hr⁻¹, about10.0 hr⁻¹, or any range including and in between any two of thesevalues.

The process may include contacting the catalyst with H₂ prior tocontacting the feedstock and H₂. Contacting the catalyst with H₂ priorto contacting the feedstock and H₂ may include any one or more of thetemperatures, pressures, or LSHVs previously described.

The examples herein are provided to illustrate advantages of the presenttechnology and to further assist a person of ordinary skill in the artwith preparing or using the present technology. The examples herein arealso presented in order to more fully illustrate the preferred aspectsof the present technology. The examples should in no way be construed aslimiting the scope of the present technology, as defined by the appendedclaims. The examples can include or incorporate any of the variations,aspects or aspects of the present technology described above. Thevariations, aspects or aspects described above may also further eachinclude or incorporate the variations of any or all other variations,aspects or aspects of the present technology.

EXAMPLES

While certain embodiments have been illustrated and described, a personwith ordinary skill in the art, after reading the foregoingspecification, can effect changes, substitutions of equivalents andother types of alterations to the compounds of the present technology orsalts, pharmaceutical compositions, derivatives, prodrugs, metabolites,tautomers or racemic mixtures thereof as set forth herein. Each aspectand embodiment described above can also have included or incorporatedtherewith such variations or aspects as disclosed in regard to any orall of the other aspects and embodiments.

Preparation of Catalysts. The catalysts were prepare by wet-mixing ofmixed metal oxide powders with calcium hydroxide, Attagel-30 clay andNalco or Akzo silica sol using a Littleford plow mixer. Zusoplast PS-1,a polysaccharide extrusion aid, was also included in the wet mix. Thecomposition of the mixed metal oxide powders was as follows: the CuMnpowder was 60 wt % CuO, 30 wt % Al₂O₃, and 10 wt % MnO₂; the CuZn powderwas 36 wt % CuO, 26 wt % Al₂O₃, and 38 wt % ZnO. Table 1 provides theadded components and respective weights (in grams) for generating eachcatalyst wet mix.

TABLE 1 Wet Mix Wet Mix for Wet Mix for CuMn-1 CuMn-2 for CuZn-1 CuMnpowder 500 (calcined at 650° C.) CuMn powder 500 (calcined at 800° C.)CuZn powder 500 (calcined at 600° C.) Calcium hydroxide 71 71 71 Attagel30 clay 73 73 73 Zusoplast PS 1 29 29 29 Silica sol 265 265 265 H₂O(deionized) 265 235 235In each case, the wet-mix was extruded through a 1 inch diameter diewith a trilobe shape. Each extrudate was then calcined, providingcatalysts with a diameter of about 1.5 millimeters.

Composition of Exemplary Catalysts and a Comparative CuCrMn Catalyst.The compositions and properties of the resulting CuMn-1, CuMn-2, andCuZn-1 catalysts are provided in Table 2 below, as measured by ICP/AESand XRF (limit of detection about 0.1 wt %). A 1.5 mm diameter CuCrMnextrudate (CuCrMn catalyst) was also prepared as a comparative example.

TABLE 2 CuCrMn CuMn-1 CuMn-2 CuZn-1 (comparative) CuO (wt %) 42 39 25 39Cr₂O₃ (wt %) N.D. N.D. N.D. 33 MnO₂ (wt %) 7 8 N.D. 4 ZnO₂ (wt %) N.D.N.D. 27 N.D. Al₂O₃ (wt %) 21 21 18 SiO₂ (wt %) 19 19 21 19 CaO (wt %) 88 8 Na₂O (wt %) N.D. N.D. N.D. N.D. Cu dispersion (%) 1.4 not not notmeasured measured measured % Loss on ignition 0.8 not not not measuredmeasured measured BET surface area 16 48 22 46 (m²/g) Hg pore volume0.26 0.60 not 0.36 [10-10k A] (cc/g) measured Packed ambient 0.80 0.770.88 0.94 bulk density (g/cc) Side Crush 4.5 3.6 2.8 2 Strength (lbs/mm)N.D. = Not DetectedSodium (as Na₂O) was not detected, therefore, the level of sodium in thecompositions is less than about 0.1 wt % and may be even lower.Similarly, other compounds may be present in amounts less than about 0.1wt %.

Hydrogenolysis of a C₁₂-C₁₄ fatty acid methyl ester (C₁₆-C₁₈ FAME) feedwith CuMn-1 and a comparative CuCrMn catalyst. Hydrogenolysis of C₁₂-C₁₄fatty acid methyl ester (C₁₂-C₁₄ FAME) feed with CuMn-1 and thecomparative CuCrMn catalyst. CuMn-1 and comparative CuCrMn wereevaluated for the hydrogenolysis of a C₁₂-C₁₄ fatty acid methyl ester(C₁₂-C₁₄ FAME) feed in a fixed bed reactor using the conditionsindicated in FIG. 1 and a H₂/feed molar ratio of 250:1. The C₁₂-C₁₄ FAMEfeed exhibited an acid number of 0.5 (AN=0.6), thus indicating a freefatty acid content of 0.0005 wt %. FIG. 1 shows that the CuMn-1 of thepresent technology has a much greater activity throughout the entirecourse of the reaction. Notably, even with the normal feed, thecomparative CuCrMn catalyst shows a reduction in activity during thefirst 100 hours. Accelerated aging of each catalyst was accomplished byspiking the C₁₂-C₁₄ FAME feed with a saturated linear C₁₂ free fattyacid (n-dodecanoic acid, common name: lauric acid), namely a 0.5 wt %C₁₂ FFA spike from 100 hours to 300 hours on stream, and a 1 wt % C₁₂FFA spike from 450 hours to 500 hours. FIG. 1 shows that the CuMn-1 ofthe present technology has a slight reduction of activity during the 0.5wt % C₁₂ FFA spike and about a 10% reduction during the 1 wt % C₁₂ FFAspike, but each of these impacts reverses to about the initial activityupon discontinuing the C₁₂ FFA spike. At hour 500, the flow rate isreduced to an LHSV of 0.65 hr⁻¹ whereupon the CuMn-1 of the presenttechnology continues to perform at high conversion until the end of run.No irreversible deactivation is observable after a total of 700 hours onstream with two n-C₁₂ FFA spikes. In contrast, FIG. 1 shows the activityof the comparative CuCrMn catalyst is significantly reduced by the 0.5wt % C₁₂ FFA spike, and upon discontinuing the 0.5 wt % C₁₂ FFA spikethe CuCrMn catalyst is shown to exhibit significant irreversibledeactivation.

CuMn-2 was evaluated against a 3 mm diameter tabletted CuMn catalyst(“CuMn tablet”) for the hydrogenolysis of a C₁₂-C₁₄ FAME feed in a fixedbed reactor using the conditions indicated in FIG. 2. FIG. 2 providesthe results of the reaction at 210° C. and 230° C., where theproductivity (the moles C₁₂-C₁₄ FAME feed converted per kilogramcatalyst per hour) of the CuMn-2 catalyst of the present technology isabout 40% higher than the comparative CuMn tablet at 210° C. and almost100% higher than the comparative CuMn tablet at 210° C. Without beingbound by theory, it is believed that the higher productivity is due notonly to the higher activity of the catalysts of the present technology(as shown in FIG. 1) but also the lower packed ambient bulk density ofthe catalysts of the present technology. Thus, the catalysts of thepresent technology not only exhibit longer life but also offer a costadvantage due to the lower packed ambient bulk density.

Hydrogenolysis of a C₁₆-C₁₈ fatty acid methyl ester (C₁₆-C₁₈ FAME) feedwith CuMn-2, CuZn-1, and comparative CuCrMn catalysts. CuMn-2, CuZn-1,and the comparative CuCrMn catalyst of Table 2 were evaluated for thehydrogenolysis of a C₁₆-C₁₈ fatty acid methyl ester (C₁₆-C₁₈ FAME) feedin a fixed bed reactor using the conditions indicated in FIG. 3 and aH₂/feed molar ratio of 1000:1. The C₁₆-C₁₈ FAME feed exhibited an acidnumber of 0.6 (AN=0.6), thus indicating a free fatty acid content of0.0006 wt %. FIG. 3 shows that CuMn-2 and CuZn-1 have a higher activitythan the CuCrMn catalyst for the C₁₆-C₁₈ FAME feed. The CuCrMn catalystalso exhibits a noticeable reduction in activity during the first 120hours with the C₁₆-C₁₈ FAME feed.

Upon performing an accelerated aging experiment by spiking the C₁₆-C₁₈FAME feed with 0.5 wt % n-Cu FFA, CuMn-2 and CuZn-1 exhibit a smallreduction in conversion over the next 160 hours. This small reduction inconversion rebounds upon discontinuing the 0.5 wt % n-Cu FFA, indicatingthe small reduction in conversion was reversible for the CuMn-2 andCuZn-1 catalysts. CuMn-2 was maintained at the same conditions as uponstartup (pressure of 30 bar, a temperature of 210° C., LHSV of 0.75hr⁻¹) and continued to perform at high conversion until the end of run.Thus, after a total of 500 hours on stream that included a 160 hour 0.5wt % n-Cu FFA spike, no irreversible deactivation is observable. Inregard to CuZn-1, at hour 340 the flow rate is reduced to an LHSV of0.65 hr⁻¹ and the pressure increased to 40 bar whereupon CuZn-1 continueto perform at high conversion until the end of run. At the end of therun, after a total of 500 hours on stream that included a 160 hour 0.5wt % n-Cu FFA spike, no irreversible deactivation is observable forCuZn-1. In contrast to both CuMn-2 and CuZn-1, the CuCrMn catalystexperiences a precipitous decline in conversion upon introduction of the0.5 wt % n-Cu FFA spike.

The present technology is also not to be limited in terms of theparticular aspects described herein, which are intended as singleillustrations of individual aspects of the present technology. Manymodifications and variations of this present technology can be madewithout departing from its spirit and scope, as will be apparent tothose skilled in the art. Functionally equivalent methods within thescope of the present technology, in addition to those enumerated herein,will be apparent to those skilled in the art from the foregoingdescriptions. Such modifications and variations are intended to fallwithin the scope of the appended claims. It is to be understood thatthis present technology is not limited to particular methods, reagents,compounds, compositions, labeled compounds or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular aspects only,and is not intended to be limiting. Thus, it is intended that thespecification be considered as exemplary only with the breadth, scopeand spirit of the present technology indicated only by the appendedclaims, definitions therein and any equivalents thereof.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms “comprising,” “including,” “containing,” etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group. Each of the narrowerspecies and subgeneric groupings falling within the generic disclosurealso form part of the invention. This includes the generic descriptionof the invention with a proviso or negative limitation removing anysubject matter from the genus, regardless of whether or not the excisedmaterial is specifically recited herein.

All publications, patent applications, issued patents, and otherdocuments (for example, journals, articles and/or textbooks) referred toin this specification are herein incorporated by reference as if eachindividual publication, patent application, issued patent, or otherdocument was specifically and individually indicated to be incorporatedby reference in its entirety. Definitions that are contained in textincorporated by reference are excluded to the extent that theycontradict definitions in this disclosure.

Other embodiments are set forth in the following claims, along with thefull scope of equivalents to which such claims are entitled.

What is claimed is:
 1. A catalyst comprising: a mixed metal oxidecomprising Cu and Mn; an alumina; silica; and calcium; wherein thecatalyst comprises about 2 wt % to about 10 wt % Mn.
 2. The catalyst ofclaim 1, wherein the catalyst comprises a surface, and wherein thepercent of Cu at the surface in relation to total Cu content of thecatalyst is from about 0.5% to about 20%.
 3. The catalyst of claim 1,wherein the catalyst comprises about 15 wt % to about 50 wt % Cu.
 4. Thecatalyst of claim 1, wherein the mixed metal oxide further comprises Zn,and wherein the catalyst comprises about 15 wt % to about 50 wt % Zn. 5.The catalyst of claim 1, wherein the alumina is present in the catalystat about 10 wt % to about 30 wt %.
 6. The catalyst of claim 1, whereinthe silica is present in the catalyst at about 10 wt % to about 30 wt %.7. The catalyst of claim 1, wherein the calcium is present in thecatalyst at about 2 wt % to about 10 wt %.
 8. The catalyst of claim 1,wherein the catalyst comprises 0.5 wt % or less of sodium, chromium,barium, or a combination of two or more thereof.
 9. The catalyst ofclaim 1, wherein the catalyst has a Brunauer-Emmett-Teller surface areafrom about 10 m²/g to about 150 m²/g.
 10. The catalyst of claim 1,wherein the catalyst has a mercury pore volume from about 0.10 cm³/g toabout 0.80 cm³/g.
 11. The catalyst of claim 1, wherein the catalyst hasa packed ambient bulk density from about 0.3 g/cm3 to about 1.6 g/cm³.12. The catalyst of claim 1, wherein the catalyst has a side crushstrength from about 2.5 lbs/mm to about 12 lbs/mm.
 13. A method ofmaking the catalyst of claim 1, the method comprising calcining a shapedmaterial; wherein: the shaped material is formed by shaping a paste, thepaste comprising: a mixed metal oxide comprising Cu and Mn; an alumina;a silica sol; and calcium hydroxide.
 14. A process comprisinghydrogenation and/or hydrogenolysis of a feedstock by contacting thefeedstock and H₂ with the catalyst of claim 1, wherein the feedstockcomprises at least one carbonyl group.
 15. The process of claim 14,wherein the feedstock comprises fatty acid methyl esters.